Unit 1 chapter 1

BONDING IN SOLIDS
Normally matter exists in three states solid , liquid and gaseous state. But plasma state is also
available. More than 90% of matter exists in this state. Matter can exist in one more different state in
laboratory known as Bose Einstein condensate. Matter is made up of atoms. The state of the matter
depends on the arrangement of atoms in it. Atoms can interact each other and they interact each other via
electromagnetic interaction.
There exists four types of interactions or force. They are
1) Electro magnetic interaction or force
2) Gravitational interaction or force
3) Strong interaction or force
4) Weak interaction or force
Out of which the first two comes into picture in our day today life. Gravitational interaction is very weak
and its effects are noticeable only when the interacting particles have considerable mass. Electro
magnetic interaction is the only interaction that comes in picture while we consider atoms. The force
between atoms is electro magnetic in nature.
1. FORCE BETWEEN ATOMS
In general atoms exerts some influence on its neighboring atoms. This influence can be called as
interaction or force between atoms. This interaction can be either attractive or repulsive in nature.
The group of atoms having certain definite arrangement is called a crystal. Eg NaCl crystal. NaCl
crystal is more stable than Na atoms and Cl atoms. In general it can be said that crystal is more stable than
free atoms due to its lower energy. The difference between the energy of the atoms in the free state and in
the crystal form is called binding energy of the crystal or cohesive energy of the crystal.
The force between atoms is attractive when their separation much larger than the size of atoms and
the force becomes repulsive when the separation is very small. So the net force between the atoms is the
sum of these two.
If two atoms are at a separation r the net force can be expressed as
N M
r
B
r
A
r F = ) (
Figure shows the variation for different force with inter
atomic distance between two atoms



Where A, B, M, and N are constants. When M=2 , the first
term represents the attractive force and when N=9 the second
term represents repulsive force. There exists some point at
which these two forces are equal and the net force zero. Let
this distance be r
0
the equilibrium distance between the
atoms.
There F= 0 then
N M
r
B
r
A
=
M N
M N
A
B
r or
A
B
r

\
|
= =
1
0 0
........ . .......... ) (

2. Types of bonds
There are two types of bonds:
Primary Bonds and Secondary bonds
Primary Bonds:
Primary bonds are the strongest bonds which hold atoms together. The three types of primary bonds are:
Metallic Bonds, Covalent Bonds and Ionic Bonds
Secondary Bonds:
Secondary bonds are much weaker than primary bonds and they are between molecules. They often
provide a "weak link" for deformation or fracture. Example for secondary bonds are:
Hydrogen Bonds and Van der Waals Bonds
2.1. Ionic Bond or hetro ploar bond

Ionic bond
Ionic bond is formed by the transfer of electrons between atoms.
For example, during the reaction of sodium with chlorine: sodium (on the left) loses its one
valence electron to chlorine (on the right)

2.1.1.Lewis Dot Structures: Lewis dot structures are a shorthand to represent the valence electrons of an
atom. The structures are written as the element symbol surrounded by dots that represent the valence
electrons. The Lewis structures for the elements in the first two periods of the periodic table are shown
below.

Lewis Dot Structures



Lewis structures can also be used to show bonding between atoms. The bonding electrons are placed between the
atoms and can be represented by a pair of dots or a dash (each dash represents one pair of electrons, or one bond).
Lewis structures for H
2
and O
2
are shown below.
H
2

H:H
or
H-H
O
2


Paired and unpaired electrons
If there are two electrons in the outer shell of the atom their spins will be paired that is the spins
will be anti parallel to each other. If there is only a single electron the spin will not be paired


Ionic bond with the aid of Lewis diagrams.
Electrons are transferred from an atom having one or two outer shell electrons to an atom having six or
seven outer shell electrons. Once the atoms loses an electron it becomes positively charged and the atom
that gains the electron become negatively charged. The electro static force attraction between these atoms

creates ionic bond. Either by giving or receiving electrons atoms acquire inert gas configuration. In
inert gas configuration the atoms will have two or eight electrons in their outer shells. This is a stable
configuration.
Ionic bond exists in NaCl, MgO, and MgCl
2
In NaCl compound sodium atom having atomic number 11 has one outer shell electron (1s
2
2s
2

2p
6
3s
1
). In order to release an outer shell electron certain amount of energy has to be given to the atom.
The minimum amount of energy required to release the outer most electron from an atom is
known as its first ionization energy. For sodium its equal to 5.1 eV.
When an atom receive an electron, the atom releases some amount of energy and it is known as
electron affinity of that atom. For Chlorine atom (atomic number 17 , 1s
2
2s
2
2p
6
3s
2
3p
5
) the electron
affinity is 3.6 eV
So in NaCl ionic bond formation two process occurs.
Na + 5.6eV (ionization energy) Na
+
+ e
-

Cl +e
-
Cl
-
+ 3.6 eV

(electron affinity)

In order to produce two ions from NaCl compound the net amount of energy required is 5.1-3.6=1.5eV If
this amount of energy is supplied to the NaCl compound we get two ions Na+ and Cl-

2.1.2. Properties of ionic bond
Ionic bond is fairly strong.
They have strong binding energy.
They have high melting and boiling point.
Soluble in water. Transparent in water.
Transparent to visible light.
Ionic crystals have close pack structure.
Conductivity is less. Conductivity increases with temperature due to high mobility of ions.

2.2. Covalent bond or homo polar bond (electron pair bond)
Covalent bond is formed by the sharing of unpaired outer shell or valence electrons between two atoms.
In this bonding electrons are not transferred. A covalent bond can be formed by the sharing of single pair
of electrons or more pair of electrons. If one pair of electrons are paired its bond number is said to be one
and if two pairs are their the bond number is two and so on. The distance between the nucleus of the two
bonded atoms is known as bond length. Bond length will be maximum for bond number one molecules
and bond length decreases with in increase in bond length.

2.2.1 Covalent bond in hydrogen molecule
Bond length 0.074nm and bond strength is 4.5eV. In hydrogen atom only one lectron is available (so it is
unpaired) in the outer shell. I order to achieve inert gas configuration it shares the single outer shell
electron with another hydrogen atom so that both atoms may have the same inert gas configuration having
two outer shell electrons.


Cl molecule- There are seven electrons in the outer shell of
chlorine atom of which six electrons are having their spin
paired. The seventh electron spin is unpaired and it will be
looking for a further unpaired electron. When the unpaired
electron of one chlorine atom is paired with another unpaired
electron of a chlorine atom a covalent bond is formed with
bond number one.



2.2.2. Polar and Non-polar Covalent Bonding
There are, in fact, two subtypes of covalent bonds. The H
2
molecule is a good example of the first type
of covalent bond, the non-polar or homo polar bond. Because both atoms in the H
2
molecule have an
equal attraction (or affinity) for electrons, the bonding electrons are equally shared
by the two atoms, and a non-polar covalent bond is formed. Whenever two atoms of
the same element bond together, a non-polar bond is formed. A polar bond is formed
when electrons are unequally shared between two atoms. Polar covalent bonding
occurs because one atom has a stronger affinity for electrons than the other (yet not
enough to pull the electrons away completely and form an ion). In a polar covalent
bond, the bonding electrons will spend a greater amount of time around the atom that
has the stronger affinity for electrons. A good example of a polar covalent bond is
the hydrogen-oxygen bond in the water molecule.

2.2.3. Properties of covalent bond materials
They are hard and brittle.
Binding energy is high so their melting and boiling points are high, but low compared to that of ionic
solids.
Covalent bonds are highly directional.
These bonds have saturation properties.
Covalent solids are insoluble in water. They are soluble in organic solvents.
Conductivity varies over a vide range. Some are excellent insulators eg diamond. Some are semi-
conductors eg Si, Ge. Some behaves as poor metals eg Gray tin.
Conductivity increases with temperature.
They are transparent to longer wave lengths and opaque to shorter wave lengths.

2.3. Metallic bond
Elements having one electron in the outer shell are metallic in nature ( Na, K) and the number of
outer shell electrons increases its metallic character decreases elements having 2 0r 3 outer shell electrons
are also metals eg Mg and Al. Those elements having 4 electrons in the outer shell are less metallic and so
on.
In a metal, the outer electrons are shared among all the atoms in the solid. Each atom gives up its
outer electrons and becomes slightly positively charged. The negatively charged electrons hold the metal
atoms together. Metallic bond is considered as an un saturated covalent bond. Since the electrons are free
to move, they lead to good thermal and electrical conductivity. Silver metal is shown below


Lack of oppositely charged ions in the metallic structure and lack of sufficient valence electrons to form a
true covalent bond necessitate the sharing of valence electrons by more than two atoms. Each of the atoms
of the metal contributes its valence electrons to the formation of the negative " electron cloud". These
electrons are not associated with a particular ion but are free to move among the positive metallic ions in
definite energy levels. The metallic ions are held together by virtue of their mutual attraction for the
negative electron cloud. This is illustrated schematically in Figure 2.The metallic bond may be thought of
as an extension of the covalent bond to a large number of atoms.
In metallic bond electrons are shared. The shared electrons belongs to the metal as whole but in covalent
bond shared electrons are part of two atoms.

2.3.1. Properties of metallic bond materials
They have high electrical and thermal conductivities
Metal are opaque to electromagnetic radiations in general
Metals have high optical reflection and absorption coefficients
Bonding may be weak (mercury) or strong (tungsten) . Therefore their melting points are -39C to
3410 C
Metals are crystalline in nature due to the symmetrical arrangement of positively charged ions.

3.1. Hydrogen bond
Hydrogen bond is the weak electro static attraction between the
slightly negatively charged atom of one kind to slightly positively
charged hydrogen atom. This slight positive and negative charge is
due to the unequal sharing of electrons among the atoms eg water
molecule.
Hydrogen bonds are common in covalently bonded molecules which
contain hydrogen, such as water (H
2
O). Since the bonds are primarily
covalent, the electrons are shared between the hydrogen and oxygen
atoms. However, the electrons tend to spend more time around the
oxygen atom. This leads to a small positive charge around the hydrogen
atoms, and a negative charge around the oxygen atom. When other
molecules with this type of charge transfer are nearby, the negatively
charged end of one molecule will be weakly attracted to the positively charged end of the other molecule.
The attraction is weak because the charge transfer is small.

3.2. Van der Waals bond
Van der Waals bonds are very weak compared to other types
of bonds. These bonds are especially important in noble gases
which are cooled to very low temperatures. The electrons
surrounding an atom are always moving. At any given point in
time, the electrons may be slightly shifted to one side of an
atom, giving that side a very small negative charge. This may
cause an attraction to a slightly positively charged atom
nearby, creating a very weak bond. At most temperatures,
thermal energy overwhelms the effects of Van der Waals bonds.
Van Der Waals bonding is a secondary bonding, which exists between virtually all atoms or molecules,
but its presence may not be observed if any of the three primary bonding types is present. Secondary
bonding forces arise from atomic or molecular dipoles. In essence, an electron dipole exists whenever
there is some separation of positive and negative portions of an atom or molecule. When an electron cloud
density occurs at one side of an atom or molecule during the electron flight about the nucleus, Van Der
Waals forces are generated. This creates a dipole wherein one side of the atom becomes electrically
charged and the other side has deficiency of electrons and is considerably charged positive. The atom is
distorted as shown in Figure

4. Cohesive Energy
The difference between the average energy of the atoms of a solid (especially a crystal) and that of the
free atoms. The cohesive energy is electrostatic in nature. This is the potential energy due to the
interactions between two atoms and it depends on inter atomic spacing.
The potential energy is given as

= dr r F r U ) ( ) ( (1)
Where
N M
r
B
r
A
r F = ) ( is the resultant force acting between the atoms and r is the
distance between atoms. Then U(r)
(

= dr
r
B
r
A
r U
N M
) (
( )

= dr Br Ar
N M
On integration we get
C
N
Br
M
Ar
r U
N M
+

=

1 1
) (
1 1
where C is the constant of integration
C
r N
B
r M
A
r U
N M
+
|

\
|

+
|

\
|

=
1 1
1
1
1
1
) (
C
r
b
r
a
r U
n m
+ + = ) ( where a=A/(M-1) , b= B/(N-1), m=M-1 and n=N-1
Now applying the boundary conditions , ie when r , U0 we get constant C=0
Therefore the expression for potential energy is
n m
r
b
r
a
r U + = ) (
Figure below show the variation of
potential energy as a function of inter
atomic distance.

In a bond the atoms will be separated
by an equilibrium distance known as
the inter atomic spacing and it is
denoted as r
0
At this distance the
potential energy will be minimum due
to fact that the force of attraction will
be equal to the force of repulsion.
Mathematically this minimum can be
calculated and this represented as

= 0 at r=r
0
On differentiating
the potential and equating the value to
zero we get the value of r
0

On differentiating for a second time the potential U , if the value is negative it is a maximum and
if it is positive it is a minimum

=
()

+
()

> 0
On simplification we get
( + 1) > ( + 1)

The second derivative is positive if the above condition is met
On substituting the value of r
0

( + 1) > (+ 1)

This gives n+1>m+1 and n>m So the force is electro static in nature.
The minimum of the potential energy is called the bonding energy or the cohesive energy of the
molecule.

Substituting the value of

in the above equation we get

this is the expression for cohesive energy.

4.1 Calculation of cohesive energy of NaCl molecule
Na + 5.6eV (ionization energy) Na
+
+ e
-

Cl +e
-
Cl
-
+ 3.6 eV

(electron affinity)

So the net energy required to create Na and Cl ions is equal to 1.5eV
NaCl crystal

Electro static force of attraction exists between Na and Cl
ions. When the distance between them is 0.24nm, the
potential energy of the system will be minimum. The
expression for potential energy is as follows
=

Where q is the charge of the ion and here it is equal to e the
charge of electron
e= 1.6x10
-19

0
=8.85x10
-12
farad/meter
r
0
=2.4x10
-10
m


1eV= 1.6x10
-19
jules
Substituting these values we get U= -6eV
So the total energy released in the process is 5.1-3.6-6 = -4.5eV
This is known as the bond energy or cohesive energy of the NaCl molecule
Table shows the bond energy of different crystals.
Molecule Bond length
nm
Bond energy
eV
NaI 0.271 3.1
NaBr 0.25 3.8
NaCl 0.24 4.5
NaF 0.185 4.7
KCl 0.267 4.5
LiH 0.16 2.5

Madelung Constant
A dimensionless constant which determines the electrostatic energy of a three-dimensional periodic
crystal lattice consisting of a large number of positive and negative point charges when the number and
magnitude of the charges and the nearest-neighbor distance between them is specified. The electrostatic
potential energy of a three dimensional periodic crystal lattice of positive and negative point charges q+
and q-, N(Avogadros number) in number is given by the equation
U= N(q+)(q-)
M
/(4
0
r
0
)
Where the constant
M
is called Madelung constant

Exercise questions
1) Explain the force between two atoms when they are brought together to form a molecule and make a
plot of the different forces in the molecule
2) Plot the variation of attractive potential energy, repulsive potential energy and resultant potential
energy in a molecule and hence derive an expression for cohesive energy in a molecule
3) Give a brief description of primary bonds
4) Give a brief description of secondary bonds with relevant examples and explain their major properties
Problems
1) Estimate the bond energy of NaCl molecules as formed from Na and chlorine atoms .The inter ionic
distance is 236 pm. The ionization energy of sodium is 5.14 eV and electron affinity of chlorine is 3.65
eV
Hint : EA IP Ue BE energy bond and
r
e
V + = = ... ..... ........
4
0 0
2

2) Calculate the cohesive energy of NaCl from the following data. Distance between the ion pair
r=0.281nm. Borns Repulsive exponent (n) = 9.Madelung const (A) = 1.748
Hint: |

\
|
=
n r
Ae
CE
1
1
4
0 0
2